Dyestuff-sulphonic acid of the dioxazine series



Patented Dec. 6, 1938 PATENT OFFICE DYESTUFF-SULPHONIG ACID' OF THE DI- OXAZINE SERIES Heinrich Greune and Max Thiele, Frankfort-onthe-Main-Hochst, and Gerhard Langbein, Hofheim in Taunus, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application January 20, 1936, Serial No. 59,994. In Germany January 23, 1935 1 Claim. (01. 260246) The present invention relates to dyestuff-sulphonic acids of the dioxazine series and to a process of preparing them.

We have found that valuable dyestuff-sulphonic acids are obtainable by treating a diarylamino-benzoquinone derivative of the general formula X1 wherein R and R1 represent a sulphonated diaryl, diarylether, diarylsulphide or diaryl-urea radical and X and X1 stand for hydrogen, alkyl, phenyl or halogen, with an acid or alkaline condensing agent preferably in the presence of an organic or inorganic oxidizing agent.

By treating with condensing agents of the above kind, ring closure with formation of dioxazine rings occurs; by using sulphuric acid or fuming sulphuric acid as condensing agent, further sulpho-radicals may simultaneously enter into the dyestuff molecule.

Thus, there are obtained new dyestuffs, for instance, those of the following general formula X1 wherein X and X1 represent hydrogen, halogen,

S OzOH l N Hg alkyl or phenyl, R. represents an aryl radical, R1 represents a radical of the group consisting of -aryl, -O-aryl, -S-ary1 and NH-CONH- aryl, and wherein each group R.R of the formula contains: a sulphonic acid group and Y means that the compounds may contain further sulphonic acid groups, and the salts of these compounds.

The benzoquinone derivatives used as starting materials may be made easily by condensing in water or alcohol, if desired, with addition of an I QN\ On NH. o0 NH NH.OO.NH o \N l I NHi acid-binding agent, a 1.4-benzoquinone, for in stance, benzoquinone, toluquinone, dichlorobenzoquinone, tetrachlorobenzoquinone with a sulphonic acid of an amino-diaryl, amino-diarylether, amino-diarylsulphide or amino-diarylurea or a substitutionpr'oduct thereof.

The easy accessibility of the sulphonic acids of amino diaryls, aminodiarylethers, aminodiarylsulphides or aminodiaryl-ureas, and the large number of possible components affords a large scope for the preparation of new dyestuff-sulphonic acids. The new products dye animal, vegetable and artificial fibers fast tints which, in part, have very clear shades.

The following examples serve to illustrate the invention but they are not intended to limit it thereto; the parts are by weight:

1. parts of the condensation product from 1 mol. of chloranil and .2 mols. of 4.4-diaminodiphenyl-urea-3.3-disulphonic acid (obtainable by causing the twocomponents to react in aqueous alcohol with addition of sodium acetate) are heated in 2000 parts of sulphuric acid monohydrate for 1 hour at C. The solution, which is at first red-brown gradually turns blue. After cooling, the sulphonation mixture is poured on ice. filtered with suction and the solid matter is washed until neutral with a sodium chloride solution of 15 per cent. strength. In order to complete the conversion of the dyestuff acid into the sodium salt, the residue is stirred with a sodium carbonate solution, filtered with suction and washed with sodium chloride solution until neutral.

The dyestuff has the following probable constitution S 020B 01 Y s 0202! s OzOH wherein Y means that the compound may contain further sulphonic acid groups.

It dissolves in water to a reddish-blue solution and dyes animal and vegetable fiber, as well as viscose artificial silk and mixed fabrics, clear blue tints.

2. 100 parts of the condensation product from i-amino-diphenylether 2 sulphonic acid and chloranil are introduced at ordinary temperature into 2000 parts of sulphuric acid monohydrate and the whole is heated at about C. to C.

until a test portion taken from the mixture and. diluted with water no longer becomes brown, but orange. After heating for about 3 hours, the mass is poured on ice, salted out, filtered and the solid matter is washed until neutral and dried. The dyestuff thus obtained .dyes cotton beautiful red tints.

A very similar dyestuff is obtained by treating with sulphuric acid monohydrate, as above indicated, the condensation product from 4.4-diaminodiphenylether-2-sulphonic acid and chloranil.

3. parts of the condensation product from 4-aminodiphenyl-3-sulphonic acid and chloranil, having the formula mam SOQOH By using instead of the said sulphonic acid the sulphonated 1-pheny1-4-amino-naphthalene or the sulphonated l-(para-amino-phenyD- naphthalene a dyestufi is obtained which dyes cotton and viscose artificial silk bluish violet tints.

4. Similar dyestufis are obtained by using in the foregoing examples instead of chloranil, dichlorobenzoquinone, benzoquinone or toluquinone.

We claim:

The product identical with that obtained by heating about 1 part of a compound of the formula:

w im

SOROH dissolved in about 20 parts of sulphuric acid monohydrate to a temperature such that a test of the solution poured into water gives a reddish coloration, maintaining said temperature for about two hours, and thereafter recovering the dyestufi product, said product being a dyestuif which dyes cotton and viscose artificial silk red tints.

HEINRICH GREUNE.

MAX THIELE.

GERHARD LANGBEIN. 

